- Synthesis and properties of PNA oligomers containing orotic acid derivatives
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We have investigated the incorporation of C6-derivatives of uracil into polypyrimidine peptide nucleic acid oligomers (PNA). Starting with orotic acid (uracil-6-carboxylic acid) we have prepared a PNA monomer containing the methyl orotate nucleobase which is compatible with Fmoc-based synthesis. Treatment of the resin-bound oligomers with hydroxide or amines cleanly converted the ester to an orotic acid or orotamide-containing PNA. Alternatively, the methyl orotate-containing PNA was liberated from the resin by standard acidolysis. PNA bearing a modified nucleobase was found to hybridize to both poly(rA) and poly(dA). Complexes with poly(rA) were more stable than those with poly(dA) but both were destabilized relative to an unmodified PNA. Modification of a terminal residue was tolerated better than modification of an internal position. The type of charge provided by the modification affected the complex stability. In the worst case, an internal modification was nearly as detrimental as a base mismatch. Copyright Taylor & Francis, Inc.
- Hudson,Wojciechowski
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- A 6 - chloromethyl uracil synthetic method (by machine translation)
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The invention discloses a 6 - chloromethyl uracil synthetic method, comprises the following steps: (1) esterification reaction: the orotic adding anhydrous in methanol, adds by drops two chlorine Asia sulphone, reaction 6 hours, to evaporate the solvent, the organic solvent is added, stirring at the room temperature, filtered, and dried to get the orotic acid methyl ester; (2) reduction reaction: the methyl orotic dissolved in methanol, added to the Lewis acid, adding sodium borohydride, stirring at room temperature for 12 - 16 hours, ice for acetic acid neutralization, to evaporate the solvent, the organic solvent is added, stirring at the room temperature, filtering, drying, be 6 - hydroxy methyl uracil; (3) chlorinated reaction: the 6 - hydroxy methyl uracil in the added to the organic solvent, by adding thionyl chloride and a catalytic amount of N, N - dimethyl formamide, reaction 2 hours, cooled to the room temperature, filtering, drying, be 6 - chloro methyl uracil. Synthesis method of the invention, avoids the use of toxic reagents, mild reaction conditions, cheap, high yield, and is favorable for industrial production. (by machine translation)
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Paragraph 0047
(2017/08/29)
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- Preparation method of 5-chloro-6-chloromethyluracil
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The invention provides a 5-chloro-6-chloromethyl-uracil and a preparation method thereof. The method comprises the following steps: esterifying the 6-position carboxylic acid of orotic acid used as an initial raw material, chlorinating the 5-position hydrogen, reducing the 6-position ester into a hydroxymethyl group, and carrying out a chlorination substitution reaction to obtain the target product. The preparation method has the advantages of simplicity in operation, stable process, high yield and low cost, and is suitable for industrial production.
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Paragraph 0048; 0049; 0050; 0051; 0052; 0053; 0054
(2017/09/01)
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- Synthesis of orotidine by intramolecular nucleosidation
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An intramolecular nucleosidation approach provides easy access to orotidine in high yields. Notably, orotate itself is used as a leaving group at the anomeric position. This method has the potential for facile access to derivatives of orotidine of therapeutic interest, with implications for prebiotic formation of nucleosides. This journal is
- Kim,Krishnamurthy
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p. 5618 - 5621
(2015/03/30)
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- METHOD OF CONTROLLING UNDESIRED VEGETATION
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The present invention relates to methods of controlling undesired plant growth in crops of soya through the use of certain substituted pyrimidine derivatives. It also relates to certain novel substituted pyrimidine derivatives. Effective weed control is thereby obtained, whilst at the same time achieving unexpected levels of crop safety.
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Page/Page column 18
(2010/11/17)
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- A novel route to 2,4-dianilino-substituted pyrimidines
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A method is described to couple sterically-hindered electron-poor anilines to the 4-position of the pyrimidine core using a pyrimidine-2,4-bis(trifluoromethanesulfonate).
- Leenders, Ruben,Heeres, Jan,Guillemont, Jér?me,Lewi, Paul
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scheme or table
p. 543 - 544
(2010/10/02)
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- PYRIMIDINE DERIVATIVES AND THEIR USE AS HERBICIDES
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The present invention relates to substituted pyrimidine derivatives, as well as N- oxides thereof and agriculturally acceptable salts thereof, and their use to control undesired plant growth, in particular in crops of useful plants. The invention extends to herbicidal compositions comprising such compounds, N-oxides and/or salts as well as mixtures of the same with one or more further active ingredient (such as, for example, an herbicide, fungicide, insecticide and/or plant growth regulator) and/or a safener. The invention further relates to intermediates useful in the preparation of such compounds, and to processes for their preparation.
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Page/Page column 87
(2010/09/03)
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- CHEMICAL COMPOUNDS
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The present invention relates to substituted pyrimidine derivatives of as well as N-oxides and agriculturally acceptable salts thereof, and their use to control undesired plant growth, in particular in crops of useful plants. The invention extends to herbicidal compositions comprising such compounds, N-oxides and/or salts as well as mixtures of the same with one or more further active ingredient (such as, for example, an herbicide, fungicide, insecticide and/or plant growth regulator) and/or a safener.
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Page/Page column 166-167
(2009/07/25)
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- CHEMICAL COMPOUNDS
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The present invention relates to substituted pyrimidine derivatives as well as N- oxides and agriculturally acceptable salts thereof, and their use to control undesired plant growth, in particular in crops of useful plants. The invention extends to herbicidal compositions comprising such compounds, N-oxides and/or salts as well as mixtures of the same with one or more further active ingredient (such as, for example, an herbicide, fungicide, insecticide and/or plant growth regulator) and/or a safener.
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Page/Page column 82
(2009/12/23)
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- Synthesis of substituted pyrimidine hydrazine acids (PHA) and their use in peptide recognition
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Substituted pyrimidine-hydrazine-acids (PHA) were prepared from orotic acid in five synthetic steps and high yields. Their geometry of hydrogen bond acceptor and donor sites make them suitable for the molecular recognition of peptide β-sheets. In non-protic solvents the PHA unit emits at around 420 nm after irradiation at 281 nm. The emission intensity decreases upon peptide binding and signals the binding event. Peptides consisting of PHAs and natural amino acids or a turn structure motif were prepared. The investigation of the intramolecular binding pattern by NMR spectroscopy revealed the expected interaction of the PHA and peptide β-sheet.
- Miltschitzky, Stefan,Michlova, Veronika,Stadlbauer, Stefan,Koenig, Burkhard
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p. 135 - 160
(2007/10/03)
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- The detrimental effect of orotic acid substitution in the peptide nucleic acid strand on the stability of PNA2:NA triple helices
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We have investigated the incorporation of C6 derivatives of uracil into polypyrimidine peptide nucleic acid oligomers. Starting with uracil-6-carboxylic acid (orotic acid), a peptide nucleic acid monomer compatible with Fmoc-based synthesis was prepared. This monomer then served as a convertible nucleobase whereupon treatment of the resin-bound methyl orotate containing hexamers with hydroxide or amines cleanly converted the ester to an orotic acid or orotamide-containing peptide nucleic acid. Peptide nucleic acid hexamers containing the C6-modified nucleobase hybridized to both poly(riboadenylic acid) and poly(deoxyriboadenylic acid) via triplex formation. Complexes formed with poly(riboadenylic acid) were more stable than those formed with poly(dexoyriboadenylic acid), as measured by temperature-dependent UV spectroscopy. However, both of these complexes were destabilized relative to the complexes formed by an unmodified peptide nucleic acid oligomers. Internal or doubly substituted hexamers are destabilized more strongly than a terminally substituted one, and the type of substitution (carboxamide, ester, carboxylic acid) affects the overall triplex stability. These results clearly show that incorporation of a C6-substituted uracil into polypyrimidine PNA is detrimental to triplex formation. We have also extended this chemistry to incorporate uracil-5-methylcarboxylate into a peptide nucleic acid hexamer. After on-resin conversion of the C5 ester to the 3-(N,N-dimethylamino)propylamide, significant stabilization of the triplex formed with poly(riboadenylic acid) was observed, which illustrates the compatibility of C5 substitution with peptide nucleic acid directed triple helix formation.
- Hudson, Robert H. E.,Wojciechowski, Filip
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p. 1731 - 1740
(2007/10/03)
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- A SELECTIVE AND EFFICIENT METHOD FOR THE DEPROTECTION OF N-BENZYLOXYMETHYL (BOM) PROTECTING GROUPS FROM PYRIMIDINE AND DIHYDROPYRIMIDINE RING SYSTEMS
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N1,N3-dibenzyloxymethyl derivatives of pyrimidines and dihydropyrimidines have been successfully deprotected by using trifluoroacetic acid (TFA).These N-BOM derivatives can be selectively removed from a variety of derivatives including nucleosides and compounds which are sensitive to base and reducing conditions.
- DeFrees, Shawn A.,Reddy, Kalakota S.,Cassady, John M.
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p. 213 - 220
(2007/10/02)
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